N,N,N',N'-Tetramethylethylenediamine → 6-(tert-butyl)-2-methyl-8H-indeno[2,1-b]thiophen-8-one

HRID 853116Notes

Reaction equation

HRID 853116 reaction equation
[C:1]([C:5]1[CH:10]=[CH:9][C:8]([C:11]2[CH:12]=[C:13]([CH3:16])[S:14][CH:15]=2)=[CH:7][CH:6]=1)([CH3:4])([CH3:3])[CH3:2].CN(CCN(C)C)C.[Li]CCCC.CN(C)[C:32](=O)[O:33]CC.[NH4+].[Cl-]>CCOCC.CCCCCC>[C:1]([C:5]1[CH:6]=[CH:7][C:8]2[C:11]3[CH:12]=[C:13]([CH3:16])[S:14][C:15]=3[C:32](=[O:33])[C:9]=2[CH:10]=1)([CH3:4])([CH3:3])[CH3:2]

Participants

8

Reactant 5

HCID 8037N,N,N',N'-TetramethylethylenediamineHCID 12709Carbamic acid, N,N-dimethyl-, ethyl esterHCID 25517Ammonium ChlorideHCID 114475724-[4-(Tert-butyl)phenyl]-2-methylthiopheneHCID 178418339Butyllithium

Product 1

HCID 118177176-(tert-butyl)-2-methyl-8H-indeno[2,1-b]thiophen-8-one

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolvent2×HCID 8058HexaneSolvent

Conditions

Temperature
-40 °C

Procedure

A solution of 2.23 g (0.01 mol) of 4-[4-(tert-butyl)phenyl]-2-methylthiophene, 2.97 mL (0.02 mol) of TMEDA in 30 mL of ether was treated with 13 mL (0.02 mol) of 1.6M BuLi in hexane under stirring at −40° C. Then the reaction mixture was allowed to warm up to r.t. and stirred for 3 h. The reaction mixture was cooled −40° C. and treated with 1.17 g (0.01 mol) of ethyl N,N-dimethylcarbamate in 10 mL of ether. Then the reaction mixture was allowed to warm up to r.t. and was stirred overnight. Resulting mixture was treated with 10% aqueous NH4Cl, organic layer was separated, washed with 10% aqueous NH4Cl and then dried over anhydrous Na2SO4. Solvent was evaporated, the residue was washed with methanol. Yield 2.4 g (about 100%) of red oil.

Workup

  1. temperatureto warm up to r.t.
  2. stirringstirred for 3 h
  3. temperatureThe reaction mixture was cooled −40° C.
  4. temperatureto warm up to r.t.
  5. stirringwas stirred overnight
  6. customResulting mixture
  7. customwas separated
  8. washwashed with 10% aqueous NH4Cl
  9. dry with materialdried over anhydrous Na2SO4
  10. customSolvent was evaporated
  11. washthe residue was washed with methanol

Sources & evidence

ORD record
ord-505610f2e8ee4cdf84050ced6cd31fc9
Source dataset
uspto-grants-2007_08
Patent number
US07253292B2

Reaction notes

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